Synthesis, characterization, and application of novel amphiphilic poly(D-gluconamidoethyl methacrylate)-b-polyurethane-b-poly(D-gluconamidoethyl methacrylate) triblock copolymers

Abstract

Novel amphiphilic ABA-type poly(D-gluconamidoethyl methacrylate)-b- polyurethane-b-poly(D-gluconamidoethyl methacrylate) (PGAMA-b-PU-b-PGAMA) tri-block copolymers were successfully synthesized via the combination of the step-growth and copper-catalyzed atom transfer radical polymerization (ATRP). Dihydroxy polyurethane (HO-PU-OH) was synthesized by the step-growth polymerization of hexamethylene diisocyanate with poly(tetramethylene glycol). PGAMA-b-PU-b-PGAMA block copolymers were synthesized via copper-catalyzed ATRP of GAMA in N, N-dimethyl formamide at 20°C in the presence of 2, 2′-bipyridyl using Br-PU-Br as macroinitiator and characterized by 1H-NMR spectroscopy and GPC. The resulting block copolymer forms spherical micelles in water as observed in TEM study, and also supported by 1H NMR spectroscopy and light scattering. Miceller size increases with increase in hydrophilic PGAMA chain length as revealed by DLS study. The critical micellar concentration values of the resulting block copolymers increased with the increase of the chain length of the PGAMA block. Thermal properties of these block copolymers were studied by thermo-gravimetric analysis, and differential scanning calorimetric study. Spherical Ag-nanoparticles were successfully synthesized using these block copolymers as stabilizer. The dimension of Ag nanoparticle was tailored by altering the chain length of the hydrophilic block of the copolymer. A mechanism has been proposed for the formation of stable and regulated Ag nanoparticle using various chain length of hydrophilic PGAMA block of the tri-block copolymer. © 2012 Wiley Periodicals, Inc.