Starlike Branched Polyacrylamides by RAFT Polymerization—Part I: Synthesis and Characterization

[Image: see text] Starlike branched polyacrylamides (SB-PAMs) were synthesized using reversible addition–fragmentation chain transfer copolymerization of acrylamide (AM) and N,N′-methylenebis(acrylamide) (BisAM) in the presence of 3-(((benzylthio) carbonothioyl)thio)propanoic acid as a chain transfer agent, followed by chain extension with AM. The amount of incorporated BisAM in the core and the amount of AM during chain extension have been systematically varied. Core structures were achieved by incorporation of total monomer ratios [BisAM]/[AM] ranging from 0.010 to 0.143. The obtained macromolecular chain transfer agents had weight average molecular weights in the range of (2.2–7.8) × 10(3) Da and polydispersity indices between 1.2 and 15.1. Kinetic experiments were performed to investigate the extent of control of polymerization. Finally, the expansion of the core structures by chain-extension polymerization resulted in the successful preparation of high molecular weight SB-PAMs with apparent molecular weights ranging from 19 to 1250 kDa.