Coordination Chemistry inside Polymeric Nanoreactors: Metal Migration and Cross-Exchange in Amphiphilic Core-Shell Polymer LatexesReportar como inadecuado




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1

CNRS, LCC Laboratoire de Chimie de Coordination, Université de Toulouse, UPS, INPT, 205 Route de Narbonne, BP 44099, F-31077 Toulouse Cedex 4, France

2

Institut Universitaire de France, 103, bd Saint-Michel, 75005 Paris, France





*

Author to whom correspondence should be addressed.



Academic Editor: Nicolay V. Tsarevsky

Abstract A well-defined amphiphilic core-shell polymer functionalized with bisp-methoxy-phenylphosphinophenylphosphine BMOPPP in the nanogel NG core has been obtained by a convergent RAFT polymerization in emulsion. This BMOPPP@NG and the previously-reported TPP@NG TPP = triphenylphosphine and core cross-linked micelles L@CCM; L = TPP, BMOPPP having a slightly different architecture were loaded with RhacacCO2 or RhClCOD2 to yield RhacacCOL@Pol or RhClCODL@Pol Pol = CCM, NG. The interparticle metal migration from RhacacCOTPP@NG to TPP@NG is fast at natural pH and much slower at high pH, the rate not depending significantly on the polymer architecture CCM vs. NG. The cross-exchange using RhacacCOBMOPPP@Pol and RhClCODTPP@Pol Pol = CCM or NG as reagents at natural pH is also rapid ca. 1 h, although slower than the equivalent homogeneous reaction on the molecular species <5 min. On the other hand, the subsequent rearrangement of RhacacCOTPP@Pol and RhClCODTPP@Pol within the TPP@Pol core and of RhacacCOBMOPPP@Pol and RhClCODBMOPPP@Pol within the BMOPPP@Pol core, leading respectively to RhClCOTPP@Pol2 and RhClCOBMOPPP@Pol2, is much more rapid <30 min than on the corresponding homogeneous process with the molecular species >24 h. View Full-Text

Keywords: core cross-linked micelles; interparticle molecular migration; phosphine-functionalized polymers; polymer latex; RAFT polymerization; rhodium complexes core cross-linked micelles; interparticle molecular migration; phosphine-functionalized polymers; polymer latex; RAFT polymerization; rhodium complexes





Autor: Si Chen 1, Eric Manoury 1, Florence Gayet 1 and Rinaldo Poli 1,2,*

Fuente: http://mdpi.com/



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