Amphiphilic gradient poly(styrene-co-acrylic acid) copolymer prepared via nitroxide-mediated solution polymerization. Synthesis, characterization in aqueous solution and evaluation as emulsion polymerization stabilizer

A well-defined, amphiphilic poly(styrene-co-acrylic acid) copolymer was synthesized in a single step by nitroxide-mediated controlled free-radical copolymerization of styrene and acrylic acid, without protection of the acid groups: Mn=6500 g mol−1, Mw/Mn=1.5 and a composition of FAA=0.70±0.03 in acrylic acid. In addition to the good control over molar mass and molar mass distribution, the copolymer exhibited a narrow composition distribution with a slight gradient. Such copolymer was an efficient stabilizer for the emulsion polymerizations of styrene and of mixtures of methyl methacrylate and n-butyl acrylate, until 45 wt% solids. A low amount (typically 3-4 wt% based on the monomer(s)) was needed for a good stabilization. This is approximately a decade lower than the required amount of random, amphiphilic copolymers prepared via conventional free-radical polymerization. The performances were, however, below those of analogous diblock copolymers, but the great advantage is the very easy synthetic procedure.