2259 Full Paper Macromolecular Chemistry and Physics wileyonlinelibrary.com DOI: 10.1002/macp.201300385 Reverse Iodine Transfer Polymerization (RITP) of 1,1,2,2-Tetrahydroperfluorodecyl Acrylate in Supercritical Carbon Dioxide Cécile Bouilhac,* Mathieu Chirat, Christine Joly-Duhamel, Patrick Lacroix-Desmazes* Reverse iodine transfer polymerization (RITP) of 1,1,2,2-tetrahydroperfluorodecyl acrylate (FDA) is successfully performed in supercritical carbon dioxide (scCO 2 ) at 70 °C under a CO 2 pressure of 300 bar. PolyFDA (PFDA) of increasing molecular weights (from 10 000 to 100 000 g mol −1 ) is syn- thesized with good agreement between theoretical, 1 H NMR spectroscopy and and size exclu- sion chromatography/refractive index/right-angle laser-light scattering/differential viscometer (SEC/RI/RALLS/DV)-estimated molecular weights (M n ). Furthermore, the increase of M n goes with a decrease of the dispersity of the polymers ( Ð from 2.06 to 1.33), which is consistent with a controlled radical polymerization (CRP). Lastly, the structure of final PFDA and therefore the RITP process are confirmed by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS) analyses. Dr. C. Bouilhac Institut Charles Gerhardt Montpellier UMR5253 CNRS- UM2-ENSCM-UM1, Equipe Ingénierie et Architectures Macromoléculaires, Université Montpellier II cc1702, Place Eugène Bataillon, 34095, Montpellier Cedex 5, France E-mail: cecile.bouilhac@univ-montp2.fr Dr. M. Chirat, Dr. C. Joly-Duhamel, Dr. P. Lacroix-Desmazes Institut Charles Gerhardt Montpellier UMR5253 CNRS- UM2-ENSCM-UM1, Equipe Ingénierie et Architectures Macromoléculaires, Ecole Nationale Supérieure de Chimie de Montpellier, 8 Rue de l’Ecole Normale, 34296, Montpellier Cedex 5, France E-mail: patrick.lacroix-desmazes@enscm.fr the utilization of supercritical carbon dioxide (scCO 2 ) has attracted considerable interest in various fields, including in polymerization. [2–4] Indeed, scCO 2 presents the advan- tage of being inexpensive, environmentally benign, non- toxic, non-flammable and its critical temperature and pressure are easy to reach ( T C = 31 °C, P C = 73 bar). More- over, scCO 2 has a very low viscosity and a high diffusion coefficient along with densities similar to common sol- vents. The ability to tune these physical properties by slight variations of pressure or temperature is unique to supercritical fluids. The solubility of many homopolymers and copoly- mers has been studied in scCO 2 . [5–8] Thus, polymers can be categorized into either “CO 2 -philic” (such as poly(fluoroalkyl(meth)acrylate)s and silicone-based poly- mers [9] or “CO 2 -phobic” materials (conventional organic polymers, either hydrophilic such as poly( N-vinyl pyr- rolidone) or lipophilic such as polystyrene). Except a few examples (e.g., Beuermann et al. [10] have successfully synthesized polystyrene in scCO 2 via homogeneous free- radical polymerization, although they worked at rela- tively high pressure, up to 1500 bar, and the monomer 1. Introduction In recent years, “green chemistry” has been emerging as a concept going against, among others, the introduction of persistent organic pollutants into the ecosystem. [1] In this context, chemists are paying more and more atten- tion to the replacement of conventional organic solvents by environmentally friendly compounds. In particular, Macromol. Chem. Phys. 2013, 214, 2259−2265 © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim