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Enzymatic Ring‐Opening Polymerization of ε‐Caprolactone in Novel Green Solvents: from Batch Systems to Continuous Flow Mesoreactors.

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Title: Enzymatic Ring‐Opening Polymerization of ε‐Caprolactone in Novel Green Solvents: from Batch Systems to Continuous Flow Mesoreactors.
Authors: Crovetto, Tullio1 (AUTHOR), Pasquale, Andrea1 (AUTHOR), Consolini, Daniele Alessandro2 (AUTHOR), Contente, Martina Letizia2 (AUTHOR) martina.contente@unimi.it, Pellis, Alessandro1 (AUTHOR) alessandro.pellis@unige.it
Source: Macromolecular Materials & Engineering. Apr2026, Vol. 311 Issue 4, p1-11. 11p.
Subjects: Ring-opening polymerization, Continuous flow reactors, Polycaprolactone, Caprolactones, Catalysis, Nonaqueous solvents, Biomass chemicals
Abstract: The transition toward sustainable alternatives in polymeric material production is a critical step in reducing the environmental impact of the traditional plastic industry. In this work, a novel synthetic pathway for the synthesis of poly(caprolactone) (PCL) was developed combining three present day sustainable technologies: enzymatic catalysis, biomass‐derived solvents, and flow processing. The ring‐opening polymerization (ROP) of ε‐caprolactone was catalyzed by Candida antarctica lipase B (CaLB). The reaction conditions were first optimized in batch mode by tuning the amount of used monomer, initiator (0%–10%) and evaluating different reaction solvents (anisole, eucalyptol, 2,2,5,5‐tetramethyltetrahydrofuran, phenetole and 2‐methyltetrahydrofuran). The best batch conditions (no initiator and phenetole as solvent) yielding PCL with Mn up to ∼8000 g mol−1 were successfully translated to flow systems where the reaction time was dramatically reduced from 24 h to 5 min while maintaining comparable Mn value (7800 g mol−1). These findings demonstrate the potential of integrating biocatalysis, renewable solvents, and flow technology for the development of scalable, eco‐friendly processes paving the way for future innovations in sustainable polymer synthesis. [ABSTRACT FROM AUTHOR]
Copyright of Macromolecular Materials & Engineering is the property of Wiley-Blackwell 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: Enzymatic Ring‐Opening Polymerization of ε‐Caprolactone in Novel Green Solvents: from Batch Systems to Continuous Flow Mesoreactors.
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  Data: <searchLink fieldCode="JN" term="%22Macromolecular+Materials+%26+Engineering%22">Macromolecular Materials & Engineering</searchLink>. Apr2026, Vol. 311 Issue 4, p1-11. 11p.
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  Data: <searchLink fieldCode="DE" term="%22Ring-opening+polymerization%22">Ring-opening polymerization</searchLink><br /><searchLink fieldCode="DE" term="%22Continuous+flow+reactors%22">Continuous flow reactors</searchLink><br /><searchLink fieldCode="DE" term="%22Polycaprolactone%22">Polycaprolactone</searchLink><br /><searchLink fieldCode="DE" term="%22Caprolactones%22">Caprolactones</searchLink><br /><searchLink fieldCode="DE" term="%22Catalysis%22">Catalysis</searchLink><br /><searchLink fieldCode="DE" term="%22Nonaqueous+solvents%22">Nonaqueous solvents</searchLink><br /><searchLink fieldCode="DE" term="%22Biomass+chemicals%22">Biomass chemicals</searchLink>
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  Data: The transition toward sustainable alternatives in polymeric material production is a critical step in reducing the environmental impact of the traditional plastic industry. In this work, a novel synthetic pathway for the synthesis of poly(caprolactone) (PCL) was developed combining three present day sustainable technologies: enzymatic catalysis, biomass‐derived solvents, and flow processing. The ring‐opening polymerization (ROP) of ε‐caprolactone was catalyzed by Candida antarctica lipase B (CaLB). The reaction conditions were first optimized in batch mode by tuning the amount of used monomer, initiator (0%–10%) and evaluating different reaction solvents (anisole, eucalyptol, 2,2,5,5‐tetramethyltetrahydrofuran, phenetole and 2‐methyltetrahydrofuran). The best batch conditions (no initiator and phenetole as solvent) yielding PCL with Mn up to ∼8000 g mol−1 were successfully translated to flow systems where the reaction time was dramatically reduced from 24 h to 5 min while maintaining comparable Mn value (7800 g mol−1). These findings demonstrate the potential of integrating biocatalysis, renewable solvents, and flow technology for the development of scalable, eco‐friendly processes paving the way for future innovations in sustainable polymer synthesis. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
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  Data: <i>Copyright of Macromolecular Materials & Engineering is the property of Wiley-Blackwell 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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        Value: 10.1002/mame.202500332
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        Text: English
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        PageCount: 11
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      – SubjectFull: Ring-opening polymerization
        Type: general
      – SubjectFull: Continuous flow reactors
        Type: general
      – SubjectFull: Polycaprolactone
        Type: general
      – SubjectFull: Caprolactones
        Type: general
      – SubjectFull: Catalysis
        Type: general
      – SubjectFull: Nonaqueous solvents
        Type: general
      – SubjectFull: Biomass chemicals
        Type: general
    Titles:
      – TitleFull: Enzymatic Ring‐Opening Polymerization of ε‐Caprolactone in Novel Green Solvents: from Batch Systems to Continuous Flow Mesoreactors.
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            NameFull: Crovetto, Tullio
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            NameFull: Pasquale, Andrea
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            NameFull: Consolini, Daniele Alessandro
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            NameFull: Contente, Martina Letizia
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            NameFull: Pellis, Alessandro
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              M: 04
              Text: Apr2026
              Type: published
              Y: 2026
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