Highly active bifunctional dual-arm organoboron catalysts bearing cooperative intramolecular structures for the copolymerization of CO2 and epoxides

Tong, Yutao; Cheng, Ruihua; Dong, Huan; Liu, Zhen; Ye, Jinxing; Liu, Boping

doi:10.1016/j.jcou.2022.101979

Cited by 11 publications

(12 citation statements)

References 58 publications

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“…For the copolymerization of epoxides and CO 2 , Liu and co-workers developed multifunctional boron catalysts featuring six boron units tethered to two ammonium cations via an aromatic backbone . In reactions with PO, cat68 – cat70 maintained moderate catalytic activity and >99% polymer selectivity at room temperature but exhibited varying amounts of polyether formation depending on the geometry of the aromatic linker.…”

Section: Multifunctional Organocatalysts For Rocopmentioning

confidence: 99%

Multifunctional Catalysts for Ring-Opening Copolymerizations

et al. 2022

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The ring-opening copolymerization (ROCOP) of epoxides with CO2 or cyclic anhydrides is a versatile route toward synthesizing a wide range of polycarbonate and polyester copolymers. ROCOP most commonly uses binary catalyst systems comprising separate Lewis acid and nucleophilic cocatalyst components. However, the dependence on two discrete catalyst components leads to low activities at low loadings, and binary catalyst systems are prone to numerous side reactions. It was therefore proposed that covalently tethering the Lewis acid catalyst and cocatalyst together would increase both catalyst activity and selectivity in epoxide ROCOP. Since these initial efforts, many multifunctional catalysts featuring covalently tethered cationic or Lewis base cocatalyst(s) have been developed for epoxide ROCOP. This review examines multifunctional catalysts that have been developed for copolymerization of epoxides with CO2, cyclic anhydrides, carbonyl sulfide (COS), and cyclic thioanhydrides. In particular, we will assess how multifunctional catalysts’ mechanisms of operations lead to improved activity and selectivity in ROCOP.

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Section: Multifunctional Organocatalysts For Rocopmentioning

confidence: 99%

Multifunctional Catalysts for Ring-Opening Copolymerizations

et al. 2022

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“…For the process utilizing propylene oxide, the resulting copolymer contained a sizable quantity of ether linkages (<30%). 86…”

Section: Organocatalysts For Copolymerization Of Epoxides and Co2mentioning

confidence: 99%

“…For the process utilizing propylene oxide, the resulting copolymer contained a sizable quantity of ether linkages (<30%). 86 In efforts to fine-tune the physicochemical properties of CO 2 derived polymers, the sequential copolymerization of two different epoxides with CO 2 to afford triblock copolymers has been achieved employing organoboron catalysts. 79 In this manner, triblock thermoplastic elastomers with a soft central segment provided by the copolymerization of epoxides with long substituted alkyl or alkoxymethyl chains with CO 2 flanked Scheme 4 Cyclically sequential copolymerization mechanism proposed for ECH and CO 2 coupling in the presence of the tetranuclear catalyst.…”

Section: Organocatalysts For Copolymerization Of Epoxides and Comentioning

confidence: 99%

Progress in the catalytic reactions of CO₂ and epoxides to selectively provide cyclic or polymeric carbonates

Bhat

Darensbourg

2022

Green Chem.

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“…To address this issue, our group developed the recycling process of both the initiator and TEB, and more recently, direct recycling only through precipitation . In a recent addition, 9-borabicyclo(3.3.1)nonane (9-BBN)-based bifunctional catalysts − were reported as showing high activity in CHO and CO 2 copolymerization, but only moderate performance toward PO and CO 2 copolymerization. Crucially, for an effective synthesis of polycarbonate polyols in the presence of CTAs, the catalyst selected should exhibit two imperative features: demonstrate a very high activity and be tolerant of CTAs.…”

Section: Introductionmentioning

confidence: 99%

Ultra-Productive Upcycling CO₂ into Polycarbonate Polyols via Borinane-Based Bifunctional Organocatalysts

2023

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We herein report the synthesis of commercially attractive low molar mass polycarbonate polyols obtained through the ring-opening copolymerization of CO 2 and epoxides, using a series of borinane-based bifunctional organocatalysts in the presence of chain transfer agents (CTAs). These catalysts enable CO 2 /epoxide copolymerizations with high linear vs cyclic selectivity and outstanding productivity for both poly(cyclohexane carbonate) polyols (18.2 kg/g catalyst) and poly(ether propylene carbonate) polyols (1.1 kg/g catalyst). These copolymerizations exhibit all features of living processes; the molar mass of the resulting polycarbonates could be precisely controlled by varying the [monomer]/CTA ratio. The high performance of these catalysts implying a low loading shows a great potential for applications in large-scale preparation of CO 2 -based polyols.

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Highly active bifunctional dual-arm organoboron catalysts bearing cooperative intramolecular structures for the copolymerization of CO2 and epoxides

Cited by 11 publications

References 58 publications

Multifunctional Catalysts for Ring-Opening Copolymerizations

Multifunctional Catalysts for Ring-Opening Copolymerizations

Progress in the catalytic reactions of CO₂ and epoxides to selectively provide cyclic or polymeric carbonates

Ultra-Productive Upcycling CO₂ into Polycarbonate Polyols via Borinane-Based Bifunctional Organocatalysts

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Highly active bifunctional dual-arm organoboron catalysts bearing cooperative intramolecular structures for the copolymerization of CO2 and epoxides

Cited by 11 publications

References 58 publications

Multifunctional Catalysts for Ring-Opening Copolymerizations

Multifunctional Catalysts for Ring-Opening Copolymerizations

Progress in the catalytic reactions of CO2 and epoxides to selectively provide cyclic or polymeric carbonates

Ultra-Productive Upcycling CO2 into Polycarbonate Polyols via Borinane-Based Bifunctional Organocatalysts

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Progress in the catalytic reactions of CO₂ and epoxides to selectively provide cyclic or polymeric carbonates

Ultra-Productive Upcycling CO₂ into Polycarbonate Polyols via Borinane-Based Bifunctional Organocatalysts