Synthesis of Novel μ-Star Copolymers with Poly(N-Octyl Benzamide) and Poly(ε-Caprolactone) Miktoarms through Chain-Growth Condensation Polymerization, Styrenics-Assisted Atom Transfer Radical Coupling, and Ring-Opening Polymerization

Star copolymers are known to phase separate on the nanoscale, providing useful self-assembled morphologies. In this study, the authors investigate synthesis and assembly behavior of miktoarm star (mu-star) copolymers. The authors employ a new strategy for the synthesis of unprecedented mu-star copolymers presenting poly(N-octyl benzamide) (PBA) and poly(epsilon-caprolactone) (PCL) arms: a combination of chain-growth condensation polymerization, styrenics-assisted atom transfer radical coupling, and ringopening polymerization. Gel permeation chromatography, mass-analyzed laser desorption/ionization mass spectrometry, and H-1 NMR spectroscopy reveal the successful synthesis of a well-defined (PBA(11))(2)-(PCL15)(4) mu-star copolymer (M-n,M- NMR approximate to 12 620; D = 1.22). Preliminary examination of the PBA(2)PCL(4) mu-star copolymer reveals assembled nanofibers having a uniform diameter of approximate to 20 nm.