Study of Atrp Process for the Grafting of Vinyl Monomers on PVC and PVDF

STUDY OF ATRP PROCESS FOR THE GRAFTING OF VINYL MONOMERS ON PVC AND PVDF Sonia Lanzalaco, Onofrio Scialdone, Alessandro Galia, Rosalia Mauro, Flavia Lazzano Dipartimento di Ingegneria Chimica, Gestionale, Informatica, Meccanica, Viale delle Scienze, Palermo e-mail: sonia.lanzalaco@unipa.it ATRP (atom transfer radical polymerization) has been recently used to prepare graft copolymers with regularly-spaced polymer chains from polymeric macroinitiators that have pendant chemical groups containing radically transferable halogen atoms [1]. The halogen atom serves as initiation site for the polymerization of side chains. Furthermore, Matyjaszewsky and Gennaro showed that an externally applied electrochemical potential can reversibly activate the copper catalyst for this process and demonstrated the dynamic modulation of polymerization rates through electrochemical means, fostering precise temporal control over initiation, cessation, and rejuvenation of the living process [2]. Our group has recently studied the atom transfer radical graft copolymerization by using halogen macroinitiators (polyvinylidenefluoride (PVDF) and polyvinylchloride (PVC) ) in organic media and used electrochemical approach to investigate the polymer effectiveness as ATRP macroinitiator and to detect the relative population of the redox couple Cu(I)/Cu(II) during the copolymerization . In particular in order to achieve preliminary information on the grafting of polyhydroxyethylmethacrylate on PVC and PVDF catalyzed by copper complexes, a study on the behavior of the various components of the system, such as halogenated polymer (PVC or PVDF), copper catalyst (CuCl or CuBr), ligand (TPMA or Me6TREN) , was carried out by cyclic voltammetric, chronoamperometric and spectrophotometric experiments. Some grafting experiments were also carried out in the more promising operative conditions. [1] J. F. Hester, P. Banerjee, Y. Y. Won, A. Aktakul, M. H. Acar, A. M. Mayes, Macromolecules, 2002, 35, 7652. [2] A. J. D. Magenau, N. Strandwitz, A. Gennaro, K. Matyjaszewski, Science, 332 (2011) 81-84.