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Le glycérol comme base structurale de coeurs de dendrimères obtenus par addition d'oxa-Michael sur des dérivés acryliques

Abstract : Glycerol is a bio-based molecule, abundantly available, from the saponification of triglyceride and the transesterification of vegetable oils. The work described in this PhD thesis concerns the use of glycerol as structural base of dendrimer's core, in particular by oxa-Michael addition on acrylic derivatives. The surface functionalization of dendrimers by imidazolium units is explored in order to obtain an ionic liquid dendrimer (DLI) with thermosensitive properties. In the first part, the bibliographic chapter presents the methods of dendrimers synthesis involving acrylic derivatives and their applications and, in a second part, the work introduces the oxa-Michael addition of alcohols to acrylic derivatives. The second chapter deals with the synthesis of the structural base of the dendrimer core from glycerol. The reaction of acylation of glycerol with acryloyl chloride is presented as well as the various constructions of poly(estersulfide) dendrimers from glycerol triacrylate. The nucleophilic addition of glycerol to acrolein, acrylamide, acrylates and acrylonitrile has been studied. With the acrylates, the nucleophilic addition reaction is in competition with the transesterification reaction, with the exception of t-butyl acrylate, resistant in basic medium. With acrylonitrile, the synthesis of 1,2,3-tricyanoethylglycerylether was carried out without solvent in 5 hours at room temperature in the presence of an inexpensive catalyst (4 mol% sodium hydroxide) in a yield of 88% and purity of 99% without purification method. The mono- and di-cyanoethylglycerylether reaction intermediates were characterized and allowed kinetic monitoring of the reaction. The synthesis of poly(amidoamine) dendrimers from 1,2,3-tricyanoethylglycerylether is the subject of the third chapter: synthesis of generations G0 to G2,5 and characterization of dendrimers. The defects in the structure due to intramolecular cyclization have been demonstrated by HRMS for generations Gn and the half-generation dendrimers Gn+5 (n=0, 1, 2) were purified by chromatographic column. Several routes of synthesis for the synthesis of DLI with imidazolium termini are presented
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Submitted on : Wednesday, July 11, 2018 - 4:09:05 PM
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  • HAL Id : tel-01835727, version 1


Frédéric Nadeau. Le glycérol comme base structurale de coeurs de dendrimères obtenus par addition d'oxa-Michael sur des dérivés acryliques. Chimie organique. Université de Lorraine, 2017. Français. ⟨NNT : 2017LORR0357⟩. ⟨tel-01835727⟩



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