Degradable Polystyrene via the Cleavable Comonomer Approach

Autor: Noémie Gil, Baptiste Caron, Didier Siri, Julien Roche, Slim Hadiouch, Douriya Khedaioui, Stéphane Ranque, Carole Cassagne, Damien Montarnal, Didier Gigmes, Catherine Lefay, Yohann Guillaneuf
Přispěvatelé: Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Aix-Marseille Université - Faculté de pharmacie (AMU PHARM), Aix Marseille Université (AMU), Catalyse, Polymérisation, Procédés et Matériaux (CP2M), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Vecteurs - Infections tropicales et méditerranéennes (VITROME), Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Institut de Recherche Biomédicale des Armées [Brétigny-sur-Orge] (IRBA), Institut Hospitalier Universitaire Méditerranée Infection (IHU Marseille), ANR-18-CE06-0014,CKAPART,Synthèse de particules dégradables par polymérisation radicalaire en milieu dispersé(2018)
Jazyk: angličtina
Rok vydání: 2022
Předmět:
Zdroj: Macromolecules
Macromolecules, 2022, 55 (15), pp.6680-6694. ⟨10.1021/acs.macromol.2c00651⟩
ISSN: 0024-9297
1520-5835
DOI: 10.1021/acs.macromol.2c00651⟩
Popis: International audience; Polystyrene (PS) is a major commodity polymer widely used in various applications ranging from packaging to insulation thanks to its low cost, high stiffness, and transparency as well as its relatively high softening temperature. Similarly to all polymers prepared by radical polymerization, PS is constituted of a C–C backbone and thus is not degradable. To confer degradability to such materials, the copolymerization of vinyl monomers with a cyclic monomer that could undergo radical ring-opening is an efficient method to introduce purposely cleavable bonds into the polymer backbone. Dibenzo[c,e]-oxepane-5-thione (DOT) is a cyclic thionolactone monomer known for its efficient copolymerization with acrylate derivatives but so far could not be incorporated into PS backbones. From a theoretical study combining density functional theory (DFT) and kinetic models using the PREDICI software, we showed that the modification of experimental conditions could overcome these limitations and that high molar mass degradable polystyrene (Mw close to 150 000 g·mol–1) could be prepared via statistical insertion of thioester groups into the polymer backbone. This copolymerization process is compatible with conventional free radical polymerization and reversible deactivation radical polymerization (RDRP) techniques such as nitroxide mediated polymerization (NMP). Thanks to favorable reactivity ratios allowing only a few mol % of thioester units to be randomly incorporated, there was no major modification of the thermal and mechanical properties of the PS. The degradation of such PS could be performed in tetrahydrofuran (THF) at room temperature (RT) in 1 h using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as a base, leading to oligomers with Mn close to 2000 g·mol–1. We successfully demonstrate further applicability of these copolymerization systems for the phototriggered decomposition of PS in solution as well as the synthesis of cross-linked PS networks degradable into soluble side products.
Databáze: OpenAIRE
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