Lipase-catalyzed interfacial polymerization of omega-pentadecalactone in aqueous biphasic medium: A mechanistic study - Université de Lorraine Accéder directement au contenu
Article Dans Une Revue Journal of Molecular Catalysis B: Enzymatic Année : 2013

Lipase-catalyzed interfacial polymerization of omega-pentadecalactone in aqueous biphasic medium: A mechanistic study

Résumé

The synthetic activity of lipases in biphasic o/w systems was investigated with respect to their use in the synthesis of polyester chains via transesterification reactions. Lipase-catalyzed ring-opening polymerization (ROP) of pentadecalactone (omega-PDL) dispersed in water was used as a model reaction to understand the synthetic activity of lipases in biphasic o/w system. We conducted a systematic investigation of the influence of reaction conditions on the macromolecular characteristics of oligo(omega-PDL) encompassing chemical, thermophysical and colloidal properties of the reaction medium. A model was proposed assuming Michaelis-Menten interfacial kinetics followed by chain extension via lipase-catalyzed linear polycondensation. The solidification of oligo(omega)-PDL) chains with a degree of polymerization of approximately three was identified as a major factor limiting the molecular weight of obtained oligomers to similar to 870 g mol(-1), despite the fast reaction rate and complete conversion of omega-PDL. The addition of toluene into the dispersed phase at a volumetric ratio of 0.3-0.5 of toluene to omega-PDL allowed us to circumvent this problem and increase the molecular weight of obtained oligomers up to 1460 g mol(-1). The molecular weight of polymer product according to this model was thus inversely related to the weight ratio percentage of interfacial lipase PS to omega-PDL per droplet and correspondingly correlated with the activity of lipase. Taking into account all these parameters allowed increasing the molar mass of oligo(omega-PDL) from 870 g mol(-1) to 3507 g mol(-1).
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Dates et versions

hal-01498202 , version 1 (29-03-2017)

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Pabhangkon Panlawan, Pawarisa Luangthongkam, Lars O. Wiemann, Volker Sieber, Emmanuelle Marie, et al.. Lipase-catalyzed interfacial polymerization of omega-pentadecalactone in aqueous biphasic medium: A mechanistic study. Journal of Molecular Catalysis B: Enzymatic, 2013, 88, pp.69-76. ⟨10.1016/j.molcatb.2012.11.008⟩. ⟨hal-01498202⟩
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