Progress in Polymer Science 36 (2011) 845–886 Contents lists available at ScienceDirect Progress in Polymer Science journal homepage: www.elsevier.com/locate/ppolysci RAFT/MADIX polymers for the preparation of polymer/inorganic nanohybrids Mariana Beija a , Jean-Daniel Marty a,∗ , Mathias Destarac b,∗ a Laboratoire IMRCP, CNRS UMR 5623, University of Toulouse, 118 route de Narbonne, 31062 Toulouse, France b Laboratoire HFA, CNRS UMR 5069, University of Toulouse, 118 route de Narbonne, 31062 Toulouse, France article info Article history: Received 9 July 2010 Received in revised form 19 November 2010 Accepted 7 January 2011 Available online 22 January 2011 Keywords: Macromolecular engineering MADIX polymerization Nanohybrid Nanoparticle RAFT polymerization abstract Organic–inorganic hybrid nanocomposites are an emerging class of materials that hold significant promise due to their outstanding properties, which usually arise from a com- bined and/or synergistic effect of the properties of their organic and inorganic components. Despite the numerous functionalization methods described in literature, only a few of them allow precise and easy control of the chemical composition and structure of the organic shell, whereas this point is critical to control some of the nanohybrids properties such as solubility, specific interaction and so forth. In this context, reversible addition- fragmentation chain transfer polymerization/macromolecular design by interchange of xanthates (RAFT/MADIX) technology is a fantastic tool that can be easily performed in mild and “green” conditions, being compatible with a huge variety of functional monomers and providing an excellent control of the organic shell characteristics. This review aims to describe the state of the art of the use of RAFT/MADIX polymers for the preparation of these nanohybrids. After describing the most commonly used synthetic strategies for nanohy- brids preparation, the main families of polymers are discussed in view of their chemical composition (homopolymer, copolymer, ...) and/or the targeted properties (hydrophilic, hydrophobic, stimuli-responsive). The main advantages of RAFT/MADIX technology are discussed in terms of the numerous applications of those materials. © 2011 Elsevier Ltd. All rights reserved. Contents 1. Introduction ........................................................................................................................ 847 2. Preparation methods of polymer/inorganic nanohybrids ......................................................................... 850 2.1. In situ preparation .......................................................................................................... 851 2.2. Surface-initiated polymerization/“grafting from” .......................................................................... 852 2.2.1. Surface-anchored initiators ....................................................................................... 852 2.2.2. Surface-anchored CTAs ............................................................................................ 852 2.3. Post-modification/“Grafting to” ............................................................................................. 854 2.4. “Grafting through” .......................................................................................................... 855 3. RAFT/MADIX polymer/inorganic nanohybrids ..................................................................................... 855 3.1. Homopolymers and statistical copolymers ................................................................................. 857 ∗ Corresponding authors. Fax: +33 5 61 55 82 04. E-mail addresses: marianabeija@gmail.com (M. Beija), marty@chimie.ups-tlse.fr (J.-D. Marty), destarac@chimie.ups-tlse.fr (M. Destarac). 0079-6700/$ – see front matter © 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.progpolymsci.2011.01.002