Transparente Filme aus CO<sub>2</sub>‐basierten polyungesättigten Polyethercarbonaten: eine neue Synthesestrategie und schnelle Vernetzung

Subhani, Muhammad Afzal; Köhler, Burkhard; Gürtler, Christoph; Leitner, Walter; Müller, Tobias

doi:10.1002/ange.201509249

“…Ever since Inoue's pioneering work, many studies have focused on the development of novel catalytic systems. Potent catalysts comprise metal complexes (Co, Cr, Zn) with macrocyclic porphyrin, salen or β ‐diiminate‐type ligands or heterogeneous compounds, such as ternary rare‐earth metal/zinc‐dialkyl mixtures, double metal cyanide complexes (DMC) and zinc dicarboxylates …”

Section: Introductionmentioning

confidence: 99%

Catalytic Chain Transfer Copolymerization of Propylene Oxide and CO₂ using Zinc Glutarate Catalyst

Marbach

¹

,

Höfer

²

,

Bornholdt

³

et al. 2019

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Oligo and poly(propylene ether carbonate)‐polyols with molecular weights from 0.8 to over 50 kg/mol and with 60–92 mol % carbonate linkages were synthesized by chain transfer copolymerization of carbon dioxide (CO 2 ) and propylene oxide (PO) mediated by zinc glutarate. Online ‐monitoring of the polymerization revealed that the CTA controlled copolymerization has an induction time which is resulting from reversible catalyst deactivation by the CTA. Latter is neutralized after the first monomer additions. The outcome of the chain transfer reaction is a function of the carbonate content, i. e . CO 2 pressure, most likely on account of differences in mobility (diffusion) of the various polymers. Melt viscosities of poly(ether carbonate)diols with a carbonate content between 60 and 92 mol % are reported as function of the molecular weight, showing that the mobility is higher when the ether content is higher. The procedure of PO/CO 2 catalytic chain copolymerization allows tailoring the glass temperature and viscosity.

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Synthesis of Diverse Polycarbonates by Organocatalytic Copolymerization of CO₂ and Epoxides: From High Pressure and Temperature to Ambient Conditions

Zhang

¹

,

Wang

²

,

Liu

³

et al. 2021

Angewandte Chemie

6

0

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Organophosphazenes combined with triethylborane (TEB) were selected as binary organocatalyts for the copolymerization of CO2 and epoxides. Both the activity and selectivity were highly dependent on the nature of phosphazenes. 2,4,6‐Tris[tri(1‐pyrrolidinyl)‐iminophosphorane]‐1,3,5‐triazine (C3N3‐Py‐P3) with a relatively low basicity (pKa=26.5 in CD3CN) and a bulky molecular size (φ=1.3 nm) exhibited an unprecedented efficiency (TON up to 12240) and selectivity (>99 % polymer selectivity and >99 % carbonate linkages) toward copolymerization of CO2 and cyclohexene oxide (CHO), and produced CO2‐based polycarbonates (CO2‐PCs) with high molar masses (Mn up to 275.5 kDa) at 1 MPa of CO2 and 80 °C. Surprisingly, this binary catalytic system achieved efficient CO2/CHO copolymerization with TOF up to 95 h−1 at 1 atm pressure and room temperature.

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Synthesis of Diverse Polycarbonates by Organocatalytic Copolymerization of CO₂ and Epoxides: From High Pressure and Temperature to Ambient Conditions

Zhang

¹

,

Wang

²

,

Liu

³

et al. 2021

View full text Add to dashboard Cite

Organophosphazenes combined with triethylborane (TEB) were selected as binary organocatalyts for the copolymerization of CO2 and epoxides. Both the activity and selectivity were highly dependent on the nature of phosphazenes. 2,4,6‐Tris[tri(1‐pyrrolidinyl)‐iminophosphorane]‐1,3,5‐triazine (C3N3‐Py‐P3) with a relatively low basicity (pKa=26.5 in CD3CN) and a bulky molecular size (φ=1.3 nm) exhibited an unprecedented efficiency (TON up to 12240) and selectivity (>99 % polymer selectivity and >99 % carbonate linkages) toward copolymerization of CO2 and cyclohexene oxide (CHO), and produced CO2‐based polycarbonates (CO2‐PCs) with high molar masses (Mn up to 275.5 kDa) at 1 MPa of CO2 and 80 °C. Surprisingly, this binary catalytic system achieved efficient CO2/CHO copolymerization with TOF up to 95 h−1 at 1 atm pressure and room temperature.

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Transparente Filme aus CO₂‐basierten polyungesättigten Polyethercarbonaten: eine neue Synthesestrategie und schnelle Vernetzung

Cited by 3 publications

References 38 publications

Catalytic Chain Transfer Copolymerization of Propylene Oxide and CO₂ using Zinc Glutarate Catalyst

Catalytic Chain Transfer Copolymerization of Propylene Oxide and CO₂ using Zinc Glutarate Catalyst

Synthesis of Diverse Polycarbonates by Organocatalytic Copolymerization of CO₂ and Epoxides: From High Pressure and Temperature to Ambient Conditions

Synthesis of Diverse Polycarbonates by Organocatalytic Copolymerization of CO₂ and Epoxides: From High Pressure and Temperature to Ambient Conditions

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Transparente Filme aus CO2‐basierten polyungesättigten Polyethercarbonaten: eine neue Synthesestrategie und schnelle Vernetzung

Cited by 3 publications

References 38 publications

Catalytic Chain Transfer Copolymerization of Propylene Oxide and CO2 using Zinc Glutarate Catalyst

Catalytic Chain Transfer Copolymerization of Propylene Oxide and CO2 using Zinc Glutarate Catalyst

Synthesis of Diverse Polycarbonates by Organocatalytic Copolymerization of CO2 and Epoxides: From High Pressure and Temperature to Ambient Conditions

Synthesis of Diverse Polycarbonates by Organocatalytic Copolymerization of CO2 and Epoxides: From High Pressure and Temperature to Ambient Conditions

Contact Info

Product

Resources

About

Transparente Filme aus CO₂‐basierten polyungesättigten Polyethercarbonaten: eine neue Synthesestrategie und schnelle Vernetzung

Catalytic Chain Transfer Copolymerization of Propylene Oxide and CO₂ using Zinc Glutarate Catalyst

Catalytic Chain Transfer Copolymerization of Propylene Oxide and CO₂ using Zinc Glutarate Catalyst

Synthesis of Diverse Polycarbonates by Organocatalytic Copolymerization of CO₂ and Epoxides: From High Pressure and Temperature to Ambient Conditions

Synthesis of Diverse Polycarbonates by Organocatalytic Copolymerization of CO₂ and Epoxides: From High Pressure and Temperature to Ambient Conditions