Terpolymerizations of cyclohexene oxide, CO<sub>2</sub>, and isocyanates or isothiocyanates for the synthesis of poly(carbonate–urethane)s or poly(carbonate–thioimidocarbonate)s

Nakaoka, Koichi; Muranaka, Satoshi; Yamamoto, Io; Ema, Tadashi

doi:10.1039/d3py01165h

Polym. Chem.

2024

DOI: 10.1039/d3py01165h

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Terpolymerizations of cyclohexene oxide, CO₂, and isocyanates or isothiocyanates for the synthesis of poly(carbonate–urethane)s or poly(carbonate–thioimidocarbonate)s

Koichi Nakaoka,

Satoshi Muranaka,

Io Yamamoto

et al.

Abstract: Terpolymerization of cyclohexene oxide (CHO), CO2, and aryl isothiocyanates produced poly(carbonate–thioimidocarbonate)s with gradient character, while that of CHO, CO2, and aryl isocyanates furnished poly(carbonate–urethane)s with random sequences. The former underwent...

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Cited by 3 publications

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Evolution of Copolymers of Epoxides and CO₂: Catalysts, Monomers, Architectures, and Applications

Yang,

Xie,

Zhang

et al. 2024

Chem. Rev.

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The copolymerization of CO 2 and epoxides presents a transformative approach to converting greenhouse gases into aliphatic polycarbonates (CO 2 -PCs), thereby reducing the polymer industry's dependence on fossil resources. Over the past 50 years, a wide array of metallic catalysts, both heterogeneous and homogeneous, have been developed to achieve precise control over polymer selectivity, sequence, regio-, and stereoselectivity. This review details the evolution of metal-based catalysts, with a particular focus on the emergence of organoborane catalysts, and explores how these catalysts effectively address kinetic and thermodynamic challenges in CO 2 /epoxides copoly 2 merization. Advances in the synthesis of CO 2 -PCs with varied sequence and chain architectures through diverse polymerization protocols are examined, alongside the applications of functional CO 2 -PCs produced by incorporating different epoxides. The review also underscores the contributions of computational techniques to our understanding of copolymerization mechanisms and highlights recent advances in the closed-loop chemical recycling of CO 2 -sourced polycarbonates. Finally, the industrialization efforts of CO 2 -PCs are discussed, offering readers a comprehensive understanding of the evolution and future potential of epoxide copolymerization with CO 2 .

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Evolution of Copolymers of Epoxides and CO₂: Catalysts, Monomers, Architectures, and Applications

Yang,

Xie,

Zhang

et al. 2024

Chem. Rev.

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Terpolymerization of Propylene Oxide, CO₂, and p-Toluenesulfonyl Isocyanate for the Synthesis of Poly(urethane-carbonate): p-Toluenesulfonyl Isocyanate Acts as a Backbiting Suppressor

Muranaka,

Yamamoto,

Ema

2024

ACS Appl. Polym. Mater.

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Terpolymerization of propylene oxide, CO 2 , and p-toluenesulfonyl isocyanate (TsNCO) was catalyzed by bifunctional Al III porphyrin catalysts to afford polyurethane-poly(propylene carbonate), PU-PPC, with high CO 2 contents of up to 39 wt %. TsNCO acted as a backbiting suppressor at the initial stage of the terpolymerization, contributing to the selective formation of PU-PPC. In contrast to the high electrophilicity of TsNCO, the carbamate anion generated by the reaction of TsNCO with the alkoxide intermediate has modest nucleophilicity owing to the tosyl group, which allows for the smooth formation of the PU units and the subsequent elongation of the PPC units on the catalyst to selectively produce PU-PPC. Terpolymers having the PU and PPC units in a 1:1 ratio had glass transition temperature (T g ) of 86−104 °C, while those with higher PPC contents had T g values of 39−40 °C. Block copolymer PU-b-PPC, which was synthesized in a one-pot two-step manner, showed two T g values at 45 and 76 °C. Pure PU showed 10% weight loss temperature (T d 10 ) at 230 °C, while PU-PPC with high PPC contents showed T d 10 at 236−254 °C. They were degradable upon UV light irradiation and heat treatment, while they were resistant to acid. The terpolymerization strategy using TsNCO as a backbiting suppressor potentially enables one to create CO 2based polymers such as plastics and elastomers with degradability controlled by UV light or heat.

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Terpolymerization reactions of epoxides, CO₂, and the third monomers toward sustainable CO₂-based polymers with controllable chemical and physical properties

Nakaoka,

Ema

2025

Chem. Commun.

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Terpolymerizations of cyclohexene oxide, CO₂, and isocyanates or isothiocyanates for the synthesis of poly(carbonate–urethane)s or poly(carbonate–thioimidocarbonate)s

Abstract: Terpolymerization of cyclohexene oxide (CHO), CO2, and aryl isothiocyanates produced poly(carbonate–thioimidocarbonate)s with gradient character, while that of CHO, CO2, and aryl isocyanates furnished poly(carbonate–urethane)s with random sequences. The former underwent...

Cited by 3 publications

References 74 publications

Evolution of Copolymers of Epoxides and CO₂: Catalysts, Monomers, Architectures, and Applications

Evolution of Copolymers of Epoxides and CO₂: Catalysts, Monomers, Architectures, and Applications

Terpolymerization of Propylene Oxide, CO₂, and p-Toluenesulfonyl Isocyanate for the Synthesis of Poly(urethane-carbonate): p-Toluenesulfonyl Isocyanate Acts as a Backbiting Suppressor

Terpolymerization reactions of epoxides, CO₂, and the third monomers toward sustainable CO₂-based polymers with controllable chemical and physical properties

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Terpolymerizations of cyclohexene oxide, CO2, and isocyanates or isothiocyanates for the synthesis of poly(carbonate–urethane)s or poly(carbonate–thioimidocarbonate)s

Abstract: Terpolymerization of cyclohexene oxide (CHO), CO2, and aryl isothiocyanates produced poly(carbonate–thioimidocarbonate)s with gradient character, while that of CHO, CO2, and aryl isocyanates furnished poly(carbonate–urethane)s with random sequences. The former underwent...

Cited by 3 publications

References 74 publications

Evolution of Copolymers of Epoxides and CO2: Catalysts, Monomers, Architectures, and Applications

Evolution of Copolymers of Epoxides and CO2: Catalysts, Monomers, Architectures, and Applications

Terpolymerization of Propylene Oxide, CO2, and p-Toluenesulfonyl Isocyanate for the Synthesis of Poly(urethane-carbonate): p-Toluenesulfonyl Isocyanate Acts as a Backbiting Suppressor

Terpolymerization reactions of epoxides, CO2, and the third monomers toward sustainable CO2-based polymers with controllable chemical and physical properties

Contact Info

Product

Resources

About

Terpolymerizations of cyclohexene oxide, CO₂, and isocyanates or isothiocyanates for the synthesis of poly(carbonate–urethane)s or poly(carbonate–thioimidocarbonate)s

Evolution of Copolymers of Epoxides and CO₂: Catalysts, Monomers, Architectures, and Applications

Evolution of Copolymers of Epoxides and CO₂: Catalysts, Monomers, Architectures, and Applications

Terpolymerization of Propylene Oxide, CO₂, and p-Toluenesulfonyl Isocyanate for the Synthesis of Poly(urethane-carbonate): p-Toluenesulfonyl Isocyanate Acts as a Backbiting Suppressor

Terpolymerization reactions of epoxides, CO₂, and the third monomers toward sustainable CO₂-based polymers with controllable chemical and physical properties