Characterization and monomer reactivity ratios of grafted cellulose with N-(4-nitrophenyl)acrylamide and methyl methacrylate by atom transfer radical polymerization

Abstract

N-(4-nitrophenyl)acrylamide (4NPA) original monomer was synthesized and characterized by FT-IR, 1H and 13C NMR techniques. The atom transfer radical polymerization (ATRP) of 4NPA with methyl methacrylate (MMA) were performed in dimethylformamide (DMF) at 130 °C in the presence of cellulose chloroacetate (Cell.ClAc) macro initiator, Cu(I)Cl/2,2'-bipyridine catalytic system. The graft copolymers were characterized by elemental analysis, FT-IR spectra and thermal analysis. Thermal stabilities of the graft copolymers were determined by the TGA method and it was established that thermal stability of the copolymers increased with the increase of MMA units, while it decreased with the increase of 4NPA units. In order to investigate the effect of 4NPA with MMA monomer interactions on grafting, the graft copolymerization was also studied using different feed compositions, ranging from 0.15 to 0.85. The reactivity ratios of 4NPA and MMA by ATRP on cellulose were determined using the Finemann-Ross (F-R), inverted Finemann-Ross (inverted F-R), Yezrielev-Brokhina-Roskin (Y-B-R), Kelen-Tüdos (K-T) and extended Kelen-Tüdos (extended K-T) linearization methods. The reactive ratios of r1 and r2 were found to be 0.017-0.116 and 1.209-1.472, respectively. The graft copolymers on cellulose r1.r2 are close to zero.