Nouveaux procédés d’amination sélective pour la synthèse de monomères biosourcés

Alexandre Dumon
Thèse CNRS-Solvay oct 2013 - oct 2016
Impliqué dans l'ANR CD2I Shapes
environ 1 million d'€
4 ans a compter de nov 2013
5 partenaires: ENSL, E2P2L UMI 3464 CNRS/Solvay Shanghai, UCCS UMR 8181 CNRS / Univ. Lille ; Solvay ; LCS Caen

Among the various processes to prepare amines, the reaction of ammonia with alcohols is particularly attractive because of the availability of various types of alcohols and the fact that water is the main byproduct. However, to our knowledge, no industrial process is available to date for diamine production from diols due to the lack of selectivity of the current amination catalysts (operating via nucleophilic substitution and reductive amination mechanisms). To minimize both the cost and the environmental impact of such transformation, it would be highly desirable to develop selective heterogeneous catalysts and if possible processes that could be run continuously. To this aim, we will explore the potentials of borrowing hydrogen mechanisms, offering two major benefits beyond the state-of-the-art: (1) no external hydrogen supply is required as in commercial reductive amination catalysts, and (2) it avoids the direct attack of low-nucleophilic ammonia to the alcohol. The problem solving requires a multi-disciplinary approach involving experts in Heterogeneous Catalysis, Chemical & Process Engineering, Computational Chemistry, and Physical Chemistry& Spectroscopy. This proposal joins the efforts of 1 industrial and 4 academic partners (i.e. Solvay-China, E2P2L, UCCS-Lille, ENS-Lyon and LCS-Caen) towards a common goal: the development of cutting-edge heterogeneous catalysts for the direct amination of bio-sourced diols to afford the preparation of primary amines with optimal yields. The industrial partnership with a Chemical company, Solvay China (Shanghai), ensures optimum process conditions and proper translation of academic findings into a possible industrial application.
http://www.agence-nationale-recherche.fr/projet-anr/?tx_lwmsuivibilan_pi2%5BCODE%5D=ANR-13-CDII-0004