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Destarac M.,Toulouse 1 University Capitole | Destarac M.,CNRS Laboratory for Basic and Applied Heterochemistry
Macromolecular Reaction Engineering | Year: 2010

The extraordinary scientific development of controlled radical polymerization (CRP) contrasts with the very limited number of commercially available products derived from these technologies. The present comprehensive survey takes up existing public knowledge on industrial features of CRP and gives a critical point of view on its global status, and on each CRP technique in particular. The main techniques, namely RAFT/MADIX, NMP, ATRP, OCRP, OHRP and (R)ITP, are introduced. The focus is put on their current status in industry, based on selected patent literature, conference proceedings, professional press releases and technical data sheets of commercial products. This includes the industrial availability of CRP agents, the types of polymers that have been already commercialized or that are at an advanced stage of development, and the related applications and markets. The strengths and weaknesses are given for the different CRP techniques, and ways of improvements are suggested. As is often the case for strong technological breakthroughs, the CRP processes face a multitude of hurdles (at different degrees depending on the type of CRP), that must be overcome and which greatly increase the time-tomarket for polymer products compared to mature technologies. In spite of its slow development, CRP is seen as a revolutionary method to produce precisely controlled, next generation specialty polymer additives and materials. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Source


Beija M.,CNRS Laboratory for Molecular and Photochemical Reactions | Marty J.-D.,CNRS Laboratory for Molecular and Photochemical Reactions | Destarac M.,CNRS Laboratory for Basic and Applied Heterochemistry
Chemical Communications | Year: 2011

Narrowly distributed poly(N-vinyl caprolactam) obtained by the MADIX/RAFT process was used for the preparation of novel thermoresponsive gold nanoparticles presenting a sharp reversible response to temperature, which can be easily modulated near the physiological temperature by simply changing the polymer molecular weight or concentration. © The Royal Society of Chemistry. Source


Destarac M.,CNRS Laboratory for Basic and Applied Heterochemistry
Polymer Reviews | Year: 2011

There are a certain number of precautions a polymer chemist should take before undertaking a reversible addition-fragmentation chain transfer (RAFT) polymerization with a view of obtaining a polymer with controlled macromolecular characteristics (M̄n, PDI) and little or no change of rate of polymerization in comparison with conventional radical polymerization. Among them, a proper selection of the so-called R and Z groups borne by the thiocarbonyl thio skeleton of the RAFT agent is essential and is strongly dependent on the considered monomer. In this review, we introduce the basic concepts associated with the RAFT process like its mechanism and kinetics, and how the RAFT agent structure can strongly influence its reactivity and sometimes lead to undesired kinetic behaviors. © Taylor & Francis Group, LLC. Source


Liao Q.,CNRS Laboratory for Basic and Applied Heterochemistry | Saffon-Merceron N.,University Paul Sabatier | Mezailles N.,CNRS Laboratory for Basic and Applied Heterochemistry
Angewandte Chemie - International Edition | Year: 2014

Stoichiometric reduction of N2 at a Mo center stabilized by a bulky tetradentate phosphine ligand (PP3 Cy) allowed isolation of Mo-imidoamine and Mo-imido complexes. Both complexes as well as the MoII precursor are equally suitable catalysts for the synthesis of NTMS3 (TMS= trimethylsilyl) from N2, TMSCl, and electron sources. Mechanistic studies prove the involvement of a TMS radical at least in one of the catalytic steps. © 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Source


Joost M.,CNRS Laboratory for Basic and Applied Heterochemistry | Joost M.,VU University Amsterdam | Amgoune A.,CNRS Laboratory for Basic and Applied Heterochemistry | Bourissou D.,CNRS Laboratory for Basic and Applied Heterochemistry
Angewandte Chemie - International Edition | Year: 2015

For a while, the reactivity of gold complexes was largely dominated by their Lewis acid behavior. In contrast to the other transition metals, the elementary steps of organometallic chemistry - oxidative addition, reductive elimination, transmetallation, migratory insertion - have scarcely been studied in the case of gold or even remained unprecedented until recently. However, within the last few years, the ability of gold complexes to undergo these fundamental reactions has been unambiguously demonstrated, and the reactivity of gold complexes was shown to extend well beyond π-activation. In this Review, the main achievements described in this area are presented in a historical context. Particular emphasis is set on mechanistic studies and structure determination of key intermediates. The electronic and structural parameters delineating the reactivity of gold complexes are discussed, as well as the remaining challenges. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Source

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