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Mechanistic Insights into the Ring-Opening Polymerization of Cyclic Esters Catalyzed by Phosphonium Carboxybetaines and Catalyst Design.

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Title: Mechanistic Insights into the Ring-Opening Polymerization of Cyclic Esters Catalyzed by Phosphonium Carboxybetaines and Catalyst Design.
Authors: Li, Hanghang1 (AUTHOR) lhh1762520517@163.com, Xue, Wanpeng1 (AUTHOR), Zhang, Xinyue1 (AUTHOR), Ge, Siyu1 (AUTHOR), Kang, Xiaohui1 (AUTHOR) kangxh@dmu.edu.cn, Zhang, Houli1 (AUTHOR)
Source: Polymers (20734360). Mar2026, Vol. 18 Issue 5, p663. 12p.
Subjects: Ring-opening polymerization, Catalysts, Polyesters, Phosphonium compounds, Biodegradable plastics, Density functional theory, Lactones
Abstract: Aliphatic polyesters, widely used in biomedicine due to their biocompatibility and biodegradability, are typically synthesized via the ring-opening polymerization (ROP) of cyclic esters. Although traditional metal catalysts are highly active, their biological toxicity limits their applications. Organocatalysts, particularly natural organic molecules, offer safer alternatives. We explored the ROP mechanisms of cyclic esters (L-Lactide (L-LA), ε-caprolactone (ε-CL), and δ-valerolactone (δ-VL)) catalyzed by phosphonium carboxybetaines (PCBs, (PhR)3P+(CH2)2COO−, R = H(PCB), F(PCB-F) and OMe(PCB-OMe)) through density functional theory (DFT) computations. The DFT results revealed that the ROP of cyclic esters follows a bifunctional–cooperative activation mechanism, wherein the phosphonium moiety (Ph3P+(CH2)2) activates the monomer via an extensive hydrogen-bonding interaction network, and the carboxylate (COO−) serves as a proton acceptor to enhance the nucleophilicity of the initiator phenylpropanol (PPA). In contrast, unsubstituted PCB exhibited the lowest energy barrier, being consistent with the highest catalytic activity among PCB derivatives observed experimentally. Moreover, a series of novel PCB derivatives (Ph3P+(CH2)nCOO−, n = 3–6 (PCB1-PCB4)) were designed by regulating the carbon spacer length, and their catalytic performances were computationally tested. The designed catalyst PCB2 (Ph3P+(CH2)4COO−) exhibited higher activity for the ROP of L-LA, attributed to providing sufficient flexibility to minimize deformation while improving proton-accepting capability. Similarly, PCB2 also demonstrated superior catalytic activity for δ-VL and the more challenging ε-CL monomer. This work not only clarifies the intrinsic catalytic nature of these zwitterionic organocatalysts, but also provides an effective strategy for the rational design of high-performance, metal-free catalysts for the synthesis of sustainable polyesters. [ABSTRACT FROM AUTHOR]
Copyright of Polymers (20734360) is the property of MDPI and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Mechanistic Insights into the Ring-Opening Polymerization of Cyclic Esters Catalyzed by Phosphonium Carboxybetaines and Catalyst Design.
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  Data: <searchLink fieldCode="JN" term="%22Polymers+%2820734360%29%22">Polymers (20734360)</searchLink>. Mar2026, Vol. 18 Issue 5, p663. 12p.
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  Data: <searchLink fieldCode="DE" term="%22Ring-opening+polymerization%22">Ring-opening polymerization</searchLink><br /><searchLink fieldCode="DE" term="%22Catalysts%22">Catalysts</searchLink><br /><searchLink fieldCode="DE" term="%22Polyesters%22">Polyesters</searchLink><br /><searchLink fieldCode="DE" term="%22Phosphonium+compounds%22">Phosphonium compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Biodegradable+plastics%22">Biodegradable plastics</searchLink><br /><searchLink fieldCode="DE" term="%22Density+functional+theory%22">Density functional theory</searchLink><br /><searchLink fieldCode="DE" term="%22Lactones%22">Lactones</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: Aliphatic polyesters, widely used in biomedicine due to their biocompatibility and biodegradability, are typically synthesized via the ring-opening polymerization (ROP) of cyclic esters. Although traditional metal catalysts are highly active, their biological toxicity limits their applications. Organocatalysts, particularly natural organic molecules, offer safer alternatives. We explored the ROP mechanisms of cyclic esters (L-Lactide (L-LA), ε-caprolactone (ε-CL), and δ-valerolactone (δ-VL)) catalyzed by phosphonium carboxybetaines (PCBs, (PhR)3P+(CH2)2COO−, R = H(PCB), F(PCB-F) and OMe(PCB-OMe)) through density functional theory (DFT) computations. The DFT results revealed that the ROP of cyclic esters follows a bifunctional–cooperative activation mechanism, wherein the phosphonium moiety (Ph3P+(CH2)2) activates the monomer via an extensive hydrogen-bonding interaction network, and the carboxylate (COO−) serves as a proton acceptor to enhance the nucleophilicity of the initiator phenylpropanol (PPA). In contrast, unsubstituted PCB exhibited the lowest energy barrier, being consistent with the highest catalytic activity among PCB derivatives observed experimentally. Moreover, a series of novel PCB derivatives (Ph3P+(CH2)nCOO−, n = 3–6 (PCB1-PCB4)) were designed by regulating the carbon spacer length, and their catalytic performances were computationally tested. The designed catalyst PCB2 (Ph3P+(CH2)4COO−) exhibited higher activity for the ROP of L-LA, attributed to providing sufficient flexibility to minimize deformation while improving proton-accepting capability. Similarly, PCB2 also demonstrated superior catalytic activity for δ-VL and the more challenging ε-CL monomer. This work not only clarifies the intrinsic catalytic nature of these zwitterionic organocatalysts, but also provides an effective strategy for the rational design of high-performance, metal-free catalysts for the synthesis of sustainable polyesters. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Polymers (20734360) is the property of MDPI and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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      – Type: doi
        Value: 10.3390/polym18050663
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      – Code: eng
        Text: English
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      Pagination:
        PageCount: 12
        StartPage: 663
    Subjects:
      – SubjectFull: Ring-opening polymerization
        Type: general
      – SubjectFull: Catalysts
        Type: general
      – SubjectFull: Polyesters
        Type: general
      – SubjectFull: Phosphonium compounds
        Type: general
      – SubjectFull: Biodegradable plastics
        Type: general
      – SubjectFull: Density functional theory
        Type: general
      – SubjectFull: Lactones
        Type: general
    Titles:
      – TitleFull: Mechanistic Insights into the Ring-Opening Polymerization of Cyclic Esters Catalyzed by Phosphonium Carboxybetaines and Catalyst Design.
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            NameFull: Li, Hanghang
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            NameFull: Xue, Wanpeng
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            – D: 01
              M: 03
              Text: Mar2026
              Type: published
              Y: 2026
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