In this study, we succeeded in the in situ activation of nonactivated ester moieties embedded in polymer structures. Although poly(pentafluorophenyl methacrylate) (PPFPMA) can react with 2-ethylhexylamine at 50 degrees C in the presence of proton scavenger such as NEt3, such conditions were not suitable for poly(phenyl methacrylate) (PPhMA). Nevertheless, the combination of organo-activating agents, namely 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,2,4-triazole (TZ) led to a facile conversion from ester to amide for PPhMA. The reaction between PPhMA and 2-ethylhexylamine was conducted at 120 degrees C in the presence of one equivalent of TZ and three equivalents of DBU and yielded >99% ester conversion to afford corresponding polymethacrylamide derivatives as confirmed by FT-IR and H-1 NMR measurements. In addition, poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) and poly(methyl methacrylate) (PMMA) were also allowed to react with amines in the presence of the organo-activating agents with dramatically increased conversions (>70%). (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1353-1358