Methacrylate-based densely grafted copolymers were synthesized by atom transfer radical polymerization (ATRP) and activators generated by electron transfer for atom transfer radical polymerization (AGET ATRP) techniques. The linear poly(2-(2-bromoisobutyryloxy)ethyl methacrylate) PBIEM prepared by ATRP served as a macroinitiator backbone. The "grafting from" strategy was used to initiate polymerization of tert-butyl methacrylate (tBuMA) from PBIEM under ATRP and/or AGET ATRP conditions yielding densely grafted copolymers PBIEM-graft-P(tBuMA). The low polydispersity indices (PDI) of the synthesized brushes evidenced by SEC analysis were consistent with a controlled/living radical polymerization (CLRP) mechanism. The chlorine-terminated PBIEM-graft-P(tBuMA)-Cl macroinitiators were subsequently employed for chain extension with 2-(dimethylamino ethyl) methacrylate (DMAEMA) yielding densely grafted copolymers with diblock copolymer side chains PBIEM-graft-P(tBuMA)-block-PDMAEMA. Further, PBIEM macroinitiator was used to initiate the copolymerization of a binary mixture of tBuMA and DMAEMA through both ATRP and AGET ATRP initiating systems, yielding densely grafted copolymers with statistical distribution of the side chains. The reactivity ratios for random graft copolymerization of tBuMA and DMAEMA from PBIEM backbone established by three different methods (Finemann-Ross, Kelen-Tudos and Error-in-Variable) did not substantially differ from literature values for conventional free-radical copolymerization of the same monomers. Polyampholyte brushes with PMAA-stat-PDMAEMA side chains were eventually synthesized by hydrolysis of the shielding tert-butyl groups. (C) 2012 Elsevier B.V. All rights reserved.