%0 Journal Article %T Bulk Organocatalytic Synthetic Access to Statistical Copolyesters from l-Lactide and ε-Caprolactone Using Benzoic Acid %+ University of Mons [Belgium] (UMONS) %+ Laboratoire de Chimie des Polymères Organiques (LCPO) %+ Team 1 LCPO : Polymerization Catalyses & Engineering %+ Interactions moléculaires et réactivité chimique et photochimique (IMRCP) %+ P3R - Polymères de Précision par Procédés Radicalaires (P3R) %+ Nutrition, Métabolismes et Cancer (NuMeCan) %A Mezzasalma, Leila %A Harrisson, Simon %A Saba, Saad %A Loyer, Pascal %A Coulembier, Olivier %A Taton, Daniel %Z Fonds De La Recherche Scientifique - FNRS %Z European Commission %Z Institut National de la Santé et de la Recherche Médicale %Z European Regional Development Fund %Z Belgian Federal Science Policy Office %< avec comité de lecture %@ 1525-7797 %J Biomacromolecules %I American Chemical Society %V 20 %N 5 %P 1965-1974 %8 2019-05-13 %D 2019 %R 10.1021/acs.biomac.9b00190 %M 30964279 %K organocatalysis %K statistical copolymers %K lactide %K caprolactone %K copolymerization %K benzoic acid %K bulk %Z Chemical Sciences/PolymersJournal articles %X The development of synthetic strategies to produce statistical copolymers based on l-lactide (l-LA) and ε-caprolactone (CL), denoted as P(LA- stat-CL), remains highly challenging in polymer chemistry. This is due to the differing reactivity of the two monomers during their ring-opening copolymerization (ROcP). Yet, P(LA- stat-CL) materials are highly sought after as they combine the properties of both polylactide (PLA) and poly(ε-caprolactone) (PCL). Here, benzoic acid (BA), a naturally occurring, cheap, readily recyclable, and thermally stable weak acid, is shown to trigger the organocatalyzed ring-opening copolymerization (OROcP) of l-LA and CL under solvent-free conditions at 155 °C, in presence of various alcohols as initiators, with good control over molar masses and dispersities (1.11 < Đ < 1.35) of the resulting copolyesters. Various compositions can be achieved, and the formation of statistical compounds is shown through characterization by H, C, and diffusion ordered spectroscopy NMR spectroscopies and by differential scanning calorimetry, as well as through the determination of reactivity ratios ( r = 0.86, r = 0.86), using the visualization of the sum of squared residuals space method. Furthermore, this BA-OROcP process can be exploited to access metal-free PLA- b-P(LA- stat-CL)- b-PLA triblock copolymers, using a diol as an initiator. Finally, residual traces of BA remaining in P(LA- stat-CL) copolymers (<0.125 mol %) do not show any cytotoxicity toward hepatocyte-like HepaRG cells, demonstrating the safety of this organic catalyst. %G English %2 https://univ-rennes.hal.science/hal-02120885/document %2 https://univ-rennes.hal.science/hal-02120885/file/Mezzasalma%20et%20al-2019-Bulk%20Organocatalytic%20Synthetic%20Access%20to%20Statistical%20Copolyesters%20from.pdf %L hal-02120885 %U https://univ-rennes.hal.science/hal-02120885 %~ IRD %~ UNIV-TLSE3 %~ UNIV-RENNES1 %~ CNRS %~ INSA-TOULOUSE %~ INRA %~ OPENAIRE %~ STATS-UR1 %~ NUMECAN %~ INC-CNRS %~ NUMECAN-TGTC %~ UR1-UFR-SVE %~ UR1-HAL %~ UR1-SDV %~ AGREENIUM %~ TEST-UR-CSS %~ UNIV-RENNES %~ INSA-GROUPE %~ TEST-HALCNRS %~ IMRCP %~ LCPO %~ NUMECAN-METHER %~ UR1-BIO-SA %~ TOULOUSE-INP %~ UNIV-UT3 %~ UT3-INP %~ FEDERATION-FERMAT %~ UT3-TOULOUSEINP %~ TEST2-HALCNRS