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]
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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]
ISSN:14387492
DOI:10.1002/mame.202500332