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Closed-Loop Chemical Recycling of Polylactide via Glycolysis: From Water-Soluble Oligomers to High-Purity Lactide.

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Title: Closed-Loop Chemical Recycling of Polylactide via Glycolysis: From Water-Soluble Oligomers to High-Purity Lactide.
Authors: Aliev, Gadir1 (AUTHOR), Toms, Roman1 (AUTHOR), Marinichev, Matvey1 (AUTHOR), Ismailov, Daniil1 (AUTHOR), Kirshanov, Kirill1 (AUTHOR), Gervald, Alexander1 (AUTHOR)
Source: Polymers (20734360). Mar2026, Vol. 18 Issue 5, p655. 22p.
Subjects: Depolymerization, Lactides, Biodegradable plastics, Polylactic acid, Waste management, Chemical recycling, Cleaning equipment
Abstract: Polylactide (PLA) has become widely adopted across biomedical, packaging, and manufacturing sectors due to its biodegradability and renewable sourcing. However, the rapid growth in PLA consumption has created urgent challenges related to waste management and the cleaning of processing equipment. This study investigates glycolysis as a promising chemical depolymerization pathway for PLA recycling and in situ reactor cleaning. A systematic analysis of four glycolysis agents (GA) (ethylene glycol, diethylene glycol, propylene glycol, and glycerol) was performed across molar PLA:GA ratios from 1:0.125 to 1:4 at 220 °C, targeting the efficient conversion of high-molecular-weight PLA (Mn ≈ 165 kDa) into low-molecular-weight oligomers. Gel permeation chromatography (GPC) demonstrated that propylene glycol exhibited the highest depolymerization efficiency, yielding oligomers with Mn as low as 200 g·mol−1 even at minimal glycolysis agent ratios, while glycerol produced hydroxyl-rich oligomers optimal for subsequent lactide synthesis. Hydroxyl value (HV) measurements showed excellent agreement with theoretical values (<5% deviation), allowing us to make an assumption about an approximate, close to near-quantitative con-version. Glycolysis products with Mw below 400 g·mol−1 displayed excellent water solubility, making them particularly attractive for reactor cleaning applications. Using glycerol-derived (GL) oligomers (PLA:GL = 1:0.25), purified L-lactide with a melting point of 98.1 °C and high purity (>99%) was obtained through thermocatalytic depolymerization and five recrystallization cycles, as confirmed by 1H nuclear magnetic resonance (1H NMR) and differential scanning calorimetry (DSC) analyses. The recovered lactide's high purity renders it suitable for ring-opening polymerization, enabling closed-loop PLA recycling schemes. Overall, glycolysis emerges as a highly promising chemical recycling route complementary to hydrolysis and pyrolysis: propylene glycol maximizes depolymerization efficiency for cleaning applications, while glycerol optimizes oligomer functionality for lactide recovery and advanced material synthesis. Our results provide practical guidelines for selecting glycolysis agents and conditions for cleaning and recycling applications. [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: Closed-Loop Chemical Recycling of Polylactide via Glycolysis: From Water-Soluble Oligomers to High-Purity Lactide.
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  Data: &lt;searchLink fieldCode=&quot;JN&quot; term=&quot;%22Polymers+%2820734360%29%22&quot;&gt;Polymers (20734360)&lt;/searchLink&gt;. Mar2026, Vol. 18 Issue 5, p655. 22p.
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– Name: Abstract
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  Group: Ab
  Data: Polylactide (PLA) has become widely adopted across biomedical, packaging, and manufacturing sectors due to its biodegradability and renewable sourcing. However, the rapid growth in PLA consumption has created urgent challenges related to waste management and the cleaning of processing equipment. This study investigates glycolysis as a promising chemical depolymerization pathway for PLA recycling and in situ reactor cleaning. A systematic analysis of four glycolysis agents (GA) (ethylene glycol, diethylene glycol, propylene glycol, and glycerol) was performed across molar PLA:GA ratios from 1:0.125 to 1:4 at 220 &#176;C, targeting the efficient conversion of high-molecular-weight PLA (Mn ≈ 165 kDa) into low-molecular-weight oligomers. Gel permeation chromatography (GPC) demonstrated that propylene glycol exhibited the highest depolymerization efficiency, yielding oligomers with Mn as low as 200 g&#183;mol−1 even at minimal glycolysis agent ratios, while glycerol produced hydroxyl-rich oligomers optimal for subsequent lactide synthesis. Hydroxyl value (HV) measurements showed excellent agreement with theoretical values (&lt;5% deviation), allowing us to make an assumption about an approximate, close to near-quantitative con-version. Glycolysis products with Mw below 400 g&#183;mol−1 displayed excellent water solubility, making them particularly attractive for reactor cleaning applications. Using glycerol-derived (GL) oligomers (PLA:GL = 1:0.25), purified L-lactide with a melting point of 98.1 &#176;C and high purity (&gt;99%) was obtained through thermocatalytic depolymerization and five recrystallization cycles, as confirmed by 1H nuclear magnetic resonance (1H NMR) and differential scanning calorimetry (DSC) analyses. The recovered lactide&#39;s high purity renders it suitable for ring-opening polymerization, enabling closed-loop PLA recycling schemes. Overall, glycolysis emerges as a highly promising chemical recycling route complementary to hydrolysis and pyrolysis: propylene glycol maximizes depolymerization efficiency for cleaning applications, while glycerol optimizes oligomer functionality for lactide recovery and advanced material synthesis. Our results provide practical guidelines for selecting glycolysis agents and conditions for cleaning and recycling applications. [ABSTRACT FROM AUTHOR]
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  Data: &lt;i&gt;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&#39;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.&lt;/i&gt; (Copyright applies to all Abstracts.)
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      – Type: doi
        Value: 10.3390/polym18050655
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      – Code: eng
        Text: English
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        PageCount: 22
        StartPage: 655
    Subjects:
      – SubjectFull: Depolymerization
        Type: general
      – SubjectFull: Lactides
        Type: general
      – SubjectFull: Biodegradable plastics
        Type: general
      – SubjectFull: Polylactic acid
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      – SubjectFull: Waste management
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      – SubjectFull: Chemical recycling
        Type: general
      – SubjectFull: Cleaning equipment
        Type: general
    Titles:
      – TitleFull: Closed-Loop Chemical Recycling of Polylactide via Glycolysis: From Water-Soluble Oligomers to High-Purity Lactide.
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            NameFull: Marinichev, Matvey
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            NameFull: Kirshanov, Kirill
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              Text: Mar2026
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              Y: 2026
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