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Core-Cross-Linked Micelles and Amphiphilic Nanogels as Unimolecular Nanoreactors for Micellar-Type, Metal-Based Aqueous Biphasic Catalysis

Manoury, Eric and Gayet, Florence and D'Agosto, Franck and Lansalot, Muriel and Delmas, Henri and Julcour-Lebigue, Carine and Blanco, Jean-François and Barthe, Laurie and Poli, Rinaldo Core-Cross-Linked Micelles and Amphiphilic Nanogels as Unimolecular Nanoreactors for Micellar-Type, Metal-Based Aqueous Biphasic Catalysis. (2017) In: Effects of Nanoconfinement on Catalysis, Fundamental and Applied Catalysis book series. (Fundamental and Applied Catalysis). Springer, 147-172. ISBN 978-3-319-50205-2

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Official URL: https://doi.org/10.1007/978-3-319-50207-6_7


Biphasic homogeneous protocols are attractive for catalyzed transformations in industry, especially when conducted with water as the catalyst phase as exemplified by the large-scale Rhône-Poulenc/Ruhrchemie hydroformylation process, but can only be applied when the substrate is sufficiently soluble in the aqueous phase to sustain sufficiently fast mass transport. Different solutions to reduce mass transport limitations include the use of additives to increase the substrate solubility in water or increase the water/organic interface, anchoring the catalyst onto a lower critical solution temperature (LCST) polymer to implement thermomorphic behavior, and anchoring the catalyst to the hydrophobic part of surfactants or amphiphilic block copolymers that self-assemble in the form of micelles in water. The use of catalytic micelles appears as the most attractive approach but is limited by the potential formation of stable emulsions and by loss of free macromolecules during separation. These limitations are removed by cross-linking the macromolecules into a unimolecular nanoreactor. This chapter covers the emerging area of unimolecular catalytic nanoreactors, focusing on transition metal-based catalytic applications. It will also present the synthesis of new types of catalytic unimolecular nanoreactors developed in our laboratories, conceived to function on the basis of the micellar catalysis principle. These nanoreactors consist of either core-cross-linked micelle (CCM) or amphiphilic functionalized nanogels (NG). The proof of principle of their catalytic performance in the aqueous biphasic hydroformylation of 1-octene will also be presented. The catalyst confinement objective which is highlighted in this chapter is process optimization in terms of the catalyst phase recovery and recycling.

Item Type:Book Section
Uncontrolled Keywords:
Institution:French research institutions > Centre National de la Recherche Scientifique - CNRS (FRANCE)
Other partners > Ecole Supérieure de Chimie Physique et Electronique de Lyon (FRANCE)
Université de Toulouse > Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE)
Université de Toulouse > Université Toulouse III - Paul Sabatier - UT3 (FRANCE)
Other partners > Université Claude Bernard-Lyon I - UCBL (FRANCE)
Laboratory name:
French National Research Agency (ANR)
Deposited On:16 Nov 2018 13:04

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