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Core-shell nanoreactors for efficient aqueous biphasic catalysis

Zhang, Xuewei and Cardozo Perez, Andrés Fernando and Chen, Si and Zhang, Wenjing and Julcour-Lebigue, Carine and Lansalot, Muriel and Blanco, Jean-François and Gayet, Florence and Delmas, Henri and Charleux, Bernadette and Manoury, Eric and D'Agosto, Franck and Poli, Rinaldo Core-shell nanoreactors for efficient aqueous biphasic catalysis. (2014) Chemistry A European Journal, 20. 15505-15517. ISSN 1521-3765

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Official URL: https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201403819


Water-borne phosphine-functionalized core-cross-linked micelles (CCM) consisting of a hydrophobic core and a hydrophilic shell were obtained as stable latexes by reversible addition-fragmentation chain transfer (RAFT) in water in a one-pot, three-step process. Initial homogeneous aqueous-phase copolymerization of methacrylic acid (MAA) and poly(ethylene oxide) methyl ether methacrylate (PEOMA) is followed by copolymerization of styrene (S) and 4-diphenylphosphinostyrene (DPPS), yielding P(MAA-co-PEOMA)-b-P(S-co-DPPS) amphiphilic block copolymer micelles (M) by polymerization-induced self-assembly (PISA), and final micellar cross-linking with a mixture of S and diethylene glycol dimethacrylate. The CCM were characterized by dynamic light scattering and NMR spectroscopy to evaluate size, dispersity, stability, and the swelling ability of various organic substrates. Coordination of [Rh(acac)(CO)2 ] (acac=acetylacetonate) to the core-confined phosphine groups was rapid and quantitative. The CCM and M latexes were then used, in combination with [Rh(acac)(CO)2 ], to catalyze the aqueous biphasic hydroformylation of 1-octene, in which they showed high activity, recyclability, protection of the activated Rh center by the polymer scaffold, and low Rh leaching. The CCM latex gave slightly lower catalytic activity but significantly less Rh leaching than the M latex. A control experiment conducted in the presence of the sulfoxantphos ligand pointed to the action of the CCM as catalytic nanoreactors with substrate and product transport into and out of the polymer core, rather than as a surfactant in interfacial catalysis.

Item Type:Article
HAL Id:hal-01877402
Audience (journal):International peer-reviewed journal
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)
Other partners > Institut universitaire de France - IUF (FRANCE)
Université de Toulouse > Université Toulouse III - Paul Sabatier - UT3 (FRANCE)
Other partners > Université Claude Bernard-Lyon I - UCBL (FRANCE)
Laboratory name:
Deposited On:21 Sep 2018 08:42

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