Résumé
Atom Transfer Radical Polymerization (ATRP) is one breakthrough technique to obtain well-defined and controlled polymers or copolymers. However, this technique has been mainly considered in solution and alternatives such as solvent-free mechanochemistry in a ball-mill, an emerging approach for a greener and safer chemistry, is left aside as a tool for polymer synthesis. Nevertheless, mechanochemistry in a ball-mill offers many advantages and permits to avoid the use of solvent, with shorter reaction times and simplified treatment steps making it easier to recover the product of interest. Herein, interest was put onto the development of mechanochemical ARGET-ATRP conditions for the polymerization and co-polymerization of styrene derivatives with different physicochemical properties, as well as an inimer, 4-vinylbenzyl chloride. A fine tuning of the catalyst quantity and reducing agent (easily removable ascorbic acid/Na 2 CO 3 ), allowed to obtain highly practical and unique conditions in the ball-mill that gave polymers and copolymers of 20 -100 monomer units in good to excellent yields (up to > 99%), with a good control over dispersity (typically Đ < 1.5), as analyzed by 1 H NMR and size exclusion chromatography, respectively. These unprecedented conditions allowed to render null and void all considerations concerning the physical state, properties (hydrophilic, hydrophobic) and miscibility/ solubility of monomers which are key parameters in solution-based ATRP for the synthesis of polymer and copolymer.