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Biobased and Compostable Multiblock Copolymer of Poly(l-lactic acid) Containing 2,5-Furandicarboxylic Acid for Sustainable Food Packaging: The Role of Parent Homopolymers in the Composting Kinetics and Mechanism
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    Biobased and Compostable Multiblock Copolymer of Poly(l-lactic acid) Containing 2,5-Furandicarboxylic Acid for Sustainable Food Packaging: The Role of Parent Homopolymers in the Composting Kinetics and Mechanism
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    • Enrico Bianchi
      Enrico Bianchi
      Civil, Chemical, Environmental and Materials Engineering Department, University of Bologna, Via Terracini 28, 40131 Bologna, Italy
    • Giulia Guidotti
      Giulia Guidotti
      Civil, Chemical, Environmental and Materials Engineering Department, University of Bologna, Via Terracini 28, 40131 Bologna, Italy
    • Michelina Soccio*
      Michelina Soccio
      Civil, Chemical, Environmental and Materials Engineering Department, University of Bologna, Via Terracini 28, 40131 Bologna, Italy
      Interdepartmental Center for Industrial Research on Advanced Applications in Mechanical Engineering and Materials Technology, CIRI-MAM, University of Bologna, 40131 Bologna, Italy
      *Email: [email protected]
    • Valentina Siracusa
      Valentina Siracusa
      Department of Chemical Science, University of Catania, Viale A. Doria 6, 95125 Catania, Italy
    • Massimo Gazzano
      Massimo Gazzano
      Institute for Organic Synthesis and Photoreactivity, ISOF-CNR, Via Gobetti 101, 40129 Bologna, Italy
    • Elisabetta Salatelli
      Elisabetta Salatelli
      Department of Industrial Chemistry “Toso Montanari”, University of Bologna, Viale Risorgimento 4, 40136 Bologna, Italy
    • Nadia Lotti
      Nadia Lotti
      Civil, Chemical, Environmental and Materials Engineering Department, University of Bologna, Via Terracini 28, 40131 Bologna, Italy
      Interdepartmental Center for Industrial Research on Advanced Applications in Mechanical Engineering and Materials Technology, CIRI-MAM, University of Bologna, 40131 Bologna, Italy
      Interdepartmental Center for Agro-Food Research, CIRI-AGRO, University of Bologna, 40131 Bologna, Italy
      More by Nadia Lotti
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    Biomacromolecules

    Cite this: Biomacromolecules 2023, 24, 5, 2356–2368
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    https://doi.org/10.1021/acs.biomac.3c00216
    Published April 24, 2023
    Copyright © 2023 American Chemical Society

    Abstract

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    In the last years, the exponential growth in the demand of petroleum-based plastic materials, besides the extreme exploitation of nonrenewable resources, lead to the mismanagement of their disposal and to serious ecological issues related to their dispersion in the environment. Among the possible practical solutions, the design of biobased and biodegradable polymers represents one of the most innovative challenges. In such a context, the eco-design of an aromatic–aliphatic multiblock copolymer based on poly(lactic acid) and containing 2,5-furandicarboxylic acid was carried out with the aim of improving the properties of poly(l-lactic acid) for sustainable packaging applications. The synthetic method followed a novel top–down approach, starting from industrial high-molecular-weight poly(l-lactic acid) (PLLA), which was reacted with 1,5-pentanediol to get hydroxyl-terminated PLLA and then chain-extended with hydroxyl-terminated poly(pentamethylene furanoate) (PPeF-OH). The final copolymer, called P(LLA50PeF50)-CE, was subjected to molecular, structural, and thermal characterization. Tensile and gas permeability tests were also carried out. According to the results obtained, PLLA thermal stability was improved, being the range of processing temperatures widened, and its stiffness and brittleness were decreased, making the new material suitable for the realization of films for flexible packaging. The oxygen permeability of PLLA was decreased by 40% and a similar improvement was measured also for carbon dioxide. P(LLA50PeF50)-CE was found to be completely biodegraded within 60 days of composting treatment. In terms of mechanism, the blocks of PPeF and PLLA were demonstrated to undergo surface erosion and bulk hydrolysis, respectively. In terms of kinetics, PPeF blocks degraded slower than PLLA ones.

    Copyright © 2023 American Chemical Society

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    Cited By

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    This article is cited by 4 publications.

    1. Dheeraj Chandra Joshi, Utreshwar Arjun Gavhane, Manickam Jayakannan. Melt Polycondensation Strategy to Access Unexplored l-Amino Acid and Sugar Copolymers. Biomacromolecules 2024, 25 (11) , 7311-7322. https://doi.org/10.1021/acs.biomac.4c00993
    2. Atsuki Takagi, Yu-I Hsu, Hiroshi Uyama. Synthesis of High-Toughness Polyesters Using Xylose and Lactic Acid and Analysis of Their Biodegradability. ACS Applied Polymer Materials 2024, 6 (21) , 13307-13318. https://doi.org/10.1021/acsapm.4c02662
    3. Yang Yu, Huan Liu, Jinyan Li, Huijia Song, Zhiyong Wei. Tricyclic Diester and 2,5-Furandicarboxylic Acid for the Synthesis of Biobased Hydrolysis Copolyesters with High Glass Transition Temperatures. Biomacromolecules 2023, 24 (11) , 5105-5115. https://doi.org/10.1021/acs.biomac.3c00685
    4. Chiara Siracusa, Felice Quartinello, Michelina Soccio, Mattia Manfroni, Nadia Lotti, Andrea Dorigato, Georg M. Guebitz, Alessandro Pellis. On the Selective Enzymatic Recycling of Poly(pentamethylene 2,5-furanoate)/Poly(lactic acid) Blends and Multiblock Copolymers. ACS Sustainable Chemistry & Engineering 2023, 11 (26) , 9751-9760. https://doi.org/10.1021/acssuschemeng.3c01796

    Biomacromolecules

    Cite this: Biomacromolecules 2023, 24, 5, 2356–2368
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.biomac.3c00216
    Published April 24, 2023
    Copyright © 2023 American Chemical Society

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