Synthesis of magnetic polymer nanoparticles using RAFT mediated miniemulsion polymerization in presence of amphiphilic ionic liquid as surfactant

by Sourav Chakraborty

Institution: Technische Universität Dresden
Department: Fakultät Mathematik und Naturwissenschaften
Degree: PhD
Year: 2015
Record ID: 1101848
Full text PDF: http://nbn-resolving.de/urn:nbn:de:bsz:14-qucosa-164920


Polymer magnetic composite (PMC) nanoparticles have gained a large attention due to their potential use in several biomedical applications from biomedical to engineering field. Among the different heterogeneous polymerization techniques that are generally used to prepare hybrid polymer particles, miniemulsion polymerization is proved to be an efficient one. The occurrence of preferential droplet nucleation in case of miniemulsion polymerization results in a 1:1 copy of monomer droplets to the polymer particles and such a mechanistic pathway offers a suitable environment for the preparation of hybrid polymer nanoparticles in the range between 50 to 500 nm. The surfactant in miniemulsoin plays a significant role to stabilize the droplets/particles and also in the encapsulation of nanoparticles. In the present study, a new class of surfactant, called amphiphilic ionic liquid, has been employed in the field of miniemulsion. The amphiphilic ionic liquid has amazing ability to impart surface tunable characteristics to the polymer particles when present on the surface of the particles. Thus the aim of the present work is to synthesize polymer magnetic composite nanoparticles with good colloidal stability, high content of magnetic nanoparticles as well as the chance for further surface functionality. Such magnetic nanoparticles may find applications in various fields. At first, the aim of the work was to establish a suitable recipe with ionic liquid as surfactant for the execution of miniemulsion polymerization. Monodisperse polystyrene nanoparticles were possible to be synthesized reproducibly. The established recipe was utilized to carry out the synthesis of PMC nanoparticles. Iron oxide (Fe3O4) was taken as magnetic nanoparticles (MNP) and it was hydrophobized with oleic acid to disperse in styrene. The concentration of feed MNP was varied to observe its influence on the characteristics of PMC nanoparticles. Stable dispersion of magnetic polystyrene particles was possible to be synthesized up to 8 wt% feed MNP. But feeding 12 wt% MNP resulted in the development of large amount of coagulum associated with instability in the dispersion. TGA investigation confirmed a significantly lower MNP content (8.2 wt%) of the composite compared to the feed amount. TEM investigation showed inhomogeneous distribution of MNP among polystyrene particles and agglomeration of MNP was observed on the surface of polystyrene particles. Considering the inability of the single step miniemulsion polymerization for the preparation of high MNP content polymer particles, it was aimed to find a new strategy which can produce such material. Inspired from the affinity of carboxylic acid group towards the surface of MNP, it was aimed to synthesize carboxyl functionalized polystyrene which was expected to improve the interaction between polymer and magnetic nanoparticles. For this purpose, RAFT mediated miniemulsion polymerization was performed in presence of a carboxyl functionalized chain transfer agent (CTA). The colloidal stability was much…