The confirmation of the coexistence of SARA-ATRP and SET-LRP mechanisms in the grafting reaction of PEGMA 300

This study presents for the first time in the literature the polymerization of poly (ethylene glycol) methyl ether methacrylate Mn = 300 g/mol (PEGMA 300) in the presence of poly chloroethyl methacrylate-polymethylmethacrylate copolymer poly (CLEMA-MMA) that takes place by both the SARA-ATRP and SET-LRP mechanisms. The two types of polymerizations in the system are poly (PEGMA 300) grafting to the poly (CLEMA-MMA) backbone and forming a new poly (PEGMA 300), both happening in the presence of a Cu 0 wire. Polymerization reactions are controlled, as confirmed by the molecular weight evolution with the conversion, the polymerization kinetics, the possibility to obtain block-copolymers, and the narrow value of dispersity. The results demonstrated that the poly (PEGMA 300) grafting on the poly (CLEMA-MMA) polymer follows a SARA-ATRP mechanism, while the formation of a poly (PEGMA 300) homopolymer entails a SET-LRP process. The investigation methods used to highlight the two mechanisms were GPC, 1 HRMN, and UV-VIS-NIR. • The polymerization of the monomer (PEGMA 300) in the presence of poly (CLEMA-MMA) and Cu 0 . • Two types of polymers are formed: grafted poly PEGMA 300 and poly (PEGMA 300) homopolymer. • The polymerization takes place by both SARA-ATRP and SET-LRP. • The polymerization reactions are controlled. • The investigation methods used were GPC, 1 H-RMN, and UV–Vis–NIR.