Preparation of poly(N-isopropylacrylamide) brush grafted silica particles via surface-initiated atom transfer radical polymerization used for aqueous chromatography

Abstract

Thermoresponsive poly(N-isopropylacrylamide) (PNIPAAm) brushes were densely grafted onto silica surface via surface-initiated atom transfer radical polymerization (SI-ATRP). The grafting reaction started from the surfaces of 2-bromoisobutyrate-functionalized silica particles in 2-propanol aqueous solution at ambient temperature using CuCl/CuCl₂/N,N,N′,N′,N″-pentamethyldiethylenetriamine (PMDETA) as the catalytic system. Based on thermogravimetric analysis (TGA) results, the grafting amount and grafting density of PNIPAM chains on the surface of silica were calculated to be 1.29 mg/m² and 0.0215 chains/nm², respectively. The gel permeation chromatography (GPC) result showed the relatively narrow molecular weight distribution (M_w/M_n=1.21) of the grafted PNIPAAm. The modified silica particles were applied as high-performance liquid chromatography (HPLC) packing materials to successfully separate three aromatic compounds using water as mobile phase by changing column temperature. Temperature-dependent hydrophilic/hydrophobic property alteration of PNIPAAm brushes grafted on silica particles was determined with chromatographic interaction between stationary phase and analytes. Retention time was prolonged and resolution was improved with increasing temperature. Baseline separation with high resolution at relatively low temperatures was observed, demonstrating dense PNIPAAm brushes were grafted on silica surfaces.

Keywords

poly(N-isopropylacrylamide) (PNIPAAm) / atom transfer radical polymerization (ATRP) / temperature-responsive chromatography / separation