Surface-Induced ARGET ATRP for Silicon Nanoparticles with Fluorescent Polymer Brushes

Well-defined polymer brushes attached to nanoparticles offer an elegant opportunity for surface modification because of their excellent mechanical stability, functional versatility, high graft density as well as controllability of surface properties. This study aimed to prepare hybrid materials with good dispersion in different solvents, and to endow this material with certain fluorescence characteristics. Well-defined diblock copolymers poly (styrene)-b-poly (hydroxyethyl methyl acrylate)-co-poly (hydroxyethyl methyl acrylate- rhodamine B) grafted silica nanoparticles (SNPs-g-PS-b-PHEMA-co-PHEMA-RhB) hybrid materials were synthesized via surface-initiated activators regenerated by electron transfer atom transfer radical polymerization (SI-ARGET ATRP). The SNPs surfaces were modified by 3-aminopropyltriethoxysilane (KH-550) firstly, then the initiators 2-Bromoisobutyryl bromide (BIBB) was attached to SNPs surfaces through the esterification of acyl bromide groups and amidogen groups. The synthetic initiators (SNPs-Br) were further used for the SI-ARGET ATRP of styrene (St), hydroxyethyl methyl acrylate (HEMA) and hydroxyethyl methyl acrylate-rhodamine B (HEMA-RhB). The results indicated that the SI-ARGET ATRP initiator had been immobilized onto SNPs surfaces, the Br atom have located at the end of the main polymer chains, and the polymerization process possessed the characteristic of controlled/"living" polymerization. The SNPs-g-PS-b-PHEMA-co-PHEMA-RhB hybrid materials show good fluorescence performance and good dispersion in water and EtOH but aggregated in THF. This study demonstrates that the SI-ARGET ATRP provided a unique way to tune the polymer brushes structure on silica nanoparticles surface and further broaden the application of SI-ARGET ATRP.