Polymer-encapsulation of iron oxide clusters using macroRAFT block copolymers as stabilizers: tuning of the particle morphology and surface functionalization

We report the successful synthesis of superparamagnetic latex particles with a high fraction of magnetic materials and a fast magnetic response. Commercial fatty acid-modified iron oxide (IO) nanoparticles were first assembled into spherical clusters through an emulsification/solvent evaporation method. The resulting particles were stabilized with poly(2-dimethylaminoethyl methacrylate)-b-polystyrene (PDMAEMA-b-PS) amphiphilic block copolymers obtained by RAFT, and used as seeds in the emulsion copolymerization of styrene and divinylbenzene (DVB), used as cross-linking agent. The latter revealed to be key in preserving the integrity of the clusters during the emulsion polymerization reaction, and a minimum amount (i.e.10 wt%) was necessary to obtain stable latexes composed of a core of densely packed IO nanoparticles surrounded by a thin polymer shell. DVB also had a strong influence on the particle morphology as the core-shell morphology of the composite particles could be tuned with either a smooth polymer shell or a raspberry-like surface by adjusting the DVB-to-monomer weight ratio and the feeding conditions. The amphiphilic macroRAFT not only provides colloidal stability to the magnetic latexes, but also offers a versatile platform for the design of composite particles with tailored surface properties by an appropriate choice of the hydrophilic block. Our strategy was thus successfully extended to poly(acrylic acid)-b-polystyrene (PAA-b-PS) copolymers, leading to PAA-stabilized composite particles. Both kinds of IO-encapsulated particles showed superparamagnetic properties (magnetizations at saturation of 35 and 31 emu g(-1)for PDMAEMA and PAA systems, respectively), and could thus find interesting applications as magnetic carriers in the biological field due to their thermo- (for PDMAEMA) and pH- (for PDMAEMA and PAA) responsive properties.